Anion-templated silver thiolated clusters affected by carboxylate ligands

Abstract

Under the guidance of anion templates V₁₀O₂₈⁶⁻ and SO₄²⁻, the novelty of cluster assembly can be increased by using different carboxylate ligands. Herein, the synthesis, crystal structure and electrochemical properties of three anion-templated silver thiolated clusters are reported, namely V₁₀O₂₈@Ag₄₆(ⁱPrS)₂₈(CF₃CO₂)₁₂(DMF)₂ (1), V₁₀O₂₈@Ag₄₆(ⁱPrS)₃₀(CF₃CO₂)₈(PhCO₂)₂(DMF)₄ (2), and [SO₄@Ag₂₀(ⁱPrS)₁₀(PTA)₃(HPTA)₂]_n (3, H₂PTA = phthalic acid). Single-crystal X-ray diffraction analysis showed that 1 and 2 are discrete clusters V₁₀O₂₈@Ag₄₆. The addition of PhCO₂H in the second step of 1 leads to obtaining 2 with different organic shells. If the addition of H₂PTA is made, 3 with a three-dimensional (3D) structure containing the SO₄²⁻ template can be obtained. Both V₁₀O₂₈⁶⁻ and SO₄²⁻ templates were generated in situ under solvothermal conditions. This work is the first where heterogeneous silver clusters containing the V₁₀O₂₈⁶⁻ anion template protected by an isopropyl thiolate ligand and a Ag₂₀ cluster with a 3D structure are obtained. The assembly process influenced by carboxylic acid deserves to be continuously explored in the future.